Crystallization of 1alpha-Hydroxy-2-Methylene-18,19-Dinor-Homopregnacalciferol

ABSTRACT

A method of purifying 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol to obtain 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol in crystalline form using precipitation with hexane from ethyl acetate. A method of preparing 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol crystals acceptable for X-ray experiment using precipitation with hexane from benzene by diffusive exchange of the solvents is also described.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

This invention was made with government support under DK047814 awarded by the National Institutes of Health. The government has certain rights in the invention.

BACKGROUND OF THE INVENTION

The present invention relates to purification of organic compounds, and more particularly to the purification of 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol (referred to herein as “051810”) by preparing it in crystalline form.

Purification of organic compounds, especially those designated for pharmaceutical use, is of considerable importance for chemists synthesizing such compounds. Preparation of the compound usually requires many synthetic steps and, therefore, the final product can be contaminated not only with side-products derived from the last synthetic step of the procedure but also with compounds that were formed in previous steps. Even chromatographic purification, which is a very efficient but relatively time-consuming process, does not usually provide compounds which are sufficiently pure to be used as drugs.

Depending on the method used to synthesize 1α-hydroxyvitamin D compounds, different minor undesirable compounds can accompany the final product. Thus, for example, if direct C-1 hydroxylation of 5,6-trans geometric isomer of vitamin D is performed, followed by SeO₂/NMO oxidation and photochemical irradiation [see Andrews et al., J. Org. Chem. 51, 1635 (1986); Calverley et al., Tetrahedron 43, 4609 (1987); Choudry et al, J. Org. Chem. 58, 1496 (1993)], the final 1α-hydroxyvitamin D product can be contaminated with 1β-hydroxy- as well as 5,6-trans isomers. If the method consists of C-1 allylic oxidation of the 4-phenyl-1,2,4-triazoline-3,5-dione adduct of the previtamin D compound, followed by cycloreversion of the modified adduct under basic conditions [Nevinckx et al., Tetrahedron 47, 9419 (1991); Vanmaele et al, Tetrahedron 41, 141 (1985) and 40, 1179 (1994); Vanmaele et al., Tetrahedron Lett. 23. 995 (1982)], one can expect that the desired 1α-hydroxyvitamin can be contaminated with the previtamin 5(10), 6,8-triene and 1β-hydroxy isomer. One of the most useful C-1 hydroxylation methods, of very broad scope and numerous applications, is the experimentally simple procedure elaborated by Paaren et al. [see J. Org. Chem. 45, 3253 (1980) and Proc. Natl. Acad. Sci. U.S.A. 75, 2080 (1978)]. This method consists of allylic oxidation of 3,5-cyclovitamin D derivatives, readily obtained from the buffered solvolysis of vitamin D tosylates, with SeO₂/t-BuOOH and subsequent acid-catalyzed cycloreversion to the desired 1α-hydroxy compounds. Taking into account this synthetic path it is reasonable to assume that the final product can be contaminated with 1α-hydroxy epimer, 5,6-trans isomer and the previtamin D form. 1α-hydroxyvitamin D₄ is another undesirable contaminant found in 1α-hydroxyvitamin D compounds synthesized from vitamin D₂ or from ergosterol. 1α-hydroxyvitamin D₄ results from C-1 oxidation of vitamin D₄, which in turn is derived from contamination of the commercial ergosterol material. Typically, the final product may contain up to about 1.5% by weight 1α-hydroxyvitamin D₄. Thus, a purification technique that would eliminate or substantially reduce the amount of 1α-hydroxyvitamin D₄ in the final product to less than about 0.1-0.2% would be highly desirable.

The vitamin D conjugated triene system is not only heat- and light-sensitive but it is also prone to oxidation, leading to the complex mixture of very polar compounds. Oxidation usually happens when a vitamin D compound has been stored for a prolonged time. Other types of processes that can lead to a partial decomposition of vitamin D compounds consist of some water-elimination reactions; their driving force is allylic (1α-) and homoallylic (3β-) position of the hydroxy groups. The presence of such above-mentioned oxidation and elimination products can be easily detected by thin-layer chromatography.

Usually, all 1α-hydroxylation procedures require at least one chromatographic purification. However, even chromatographically purified 1α-hydroxyvitamin D compounds, although showing consistent spectroscopic data, suggesting homogeneity, do not meet the purity criteria required for therapeutic agents that can be orally, parenterally or transdermally administered. Therefore, it was evident that a suitable method of purification of the 1α-hydroxylated vitamin D compound 051810 is required.

SUMMARY OF THE INVENTION

The present invention relates to a method of purifying 051810 by means of crystallization to obtain 051810 in crystalline form. The solvent plays a crucial role in the crystallization process, and is typically an individual liquid substance or a suitable mixture of different liquids. For crystallizing 051810, the most appropriate solvent and/or solvent system is characterized by the following factors:

(1) low toxicity;

(2) low boiling point;

(3) significant dependence of solubility properties with regard to temperature (condition necessary for providing satisfactory crystallization yield); and

(4) relatively low cost.

Interestingly, hexane, so frequently used for crystallization purposes, was found less suitable as the sole solvent for crystallization of 051810. However, it was found that a mixture of ethyl acetate and hexane, was most useful for the crystallization of 051810. In particular, it was determined that a mixture of about 1% ethyl acetate with about 99% hexane (by volume) performed well. The ethyl acetate/hexane solvent mixture was also easy to remove by evaporation or other well known methods. In all cases the crystallization process occurred easily and efficiently; and the precipitated crystals were sufficiently large to assure their recovery by filtration or other means.

Accordingly, there is obtained 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol in crystalline form. The crystalline form and three dimensional structure of 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol has a molecular packing arrangement defined by space group P2 and unit cell dimensions a=4.8 Å, b=22.9 Å, c=36.1 Å, α=90°, β=90° and γ=9°.

In one embodiment, there is described a method of purifying 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol, comprising the steps of:

(a) dissolving a product containing 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol to be purified in a solvent comprising ethyl acetate;

(b) adding hexane to said solvent and dissolved product to form a mixture;

(c) cooling said mixture containing said dissolved product below ambient temperature for a sufficient amount of time to form a precipitate of 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol crystals; and

(d) separating the 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol crystals from the mixture.

In another embodiment, there is described a method of preparing 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol crystals by diffusive exchange of solvents, comprising the steps of:

(a) dissolving a product containing 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol in a first solvent comprising benzene;

(b) providing a second solvent comprising hexane;

(c) allowing said first solvent with dissolved product and said second solvent to diffuse together for a sufficient amount of time to form a precipitate of 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol crystals; and

(d) recovering the 1α-hydroxy-2-methyelene-18,19-dinor-homopregnacalciferol crystals.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an illustration of the three dimensional structure of the first crystallographic asymmetric molecule for 051810 as defined by the atomic positional parameters discovered and set forth herein;

FIG. 2 a is an illustration of the three dimensional structure of the second crystallographic asymmetric molecule for 051810 in the absence of the benzene molecule and as defined by the atomic positional parameters discovered and set forth herein;

FIG. 2 b is an illustration of the three dimensional structure of the second asymmetric molecule for 051810 in the presence of the benzene molecule and as defined by the atomic positional parameters discovered and set forth herein; and

FIG. 3 is an illustration of a ball-and-stick representation of the entire asymmetric unit for 051810.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol (051810) in crystalline form, a pharmacologically important compound, characterized by the formula I shown below:

The present invention also provides a valuable method of purification of 051810. The purification technique involves obtaining the 051810 product in crystalline form by utilizing a crystallization procedure wherein the 051810 material to be purified is dissolved using ethyl acetate as the solvent and further precipitation with hexane. Preferably a ratio of ethyl acetate and hexane is about 1:99 (by volume). Thereafter, the solvent can be removed by evaporation, with or without vacuum, or other means as is well known, or the resultant crystals may be filtered from the mother liquor. The technique can be used to purify a wide range of final products containing 051810 obtained from any known synthesis thereof, and in varying concentrations, i.e. from microgram amounts to kilogram amounts. As is well known to those skilled in this art, the amount of solvent utilized should be minimized and/or adjusted according to the amount of 051810 to be purified.

The usefulness and advantages of the present crystallization procedure is shown in the following specific Example 1. After crystallization, the precipitated material was observed under a microscope to confirm its crystalline form. Yields of crystals were relatively high and the obtained crystals showed a relatively sharp melting point of 140-145° C.

The described crystallization process of the synthetic 051810 product represents a valuable purification method, which can remove most side products derived from the synthetic path. Such impurity is the result of the contamination of starting raw materials. The crystallization process occurred easily and efficiently; and the precipitated crystals were sufficiently large to assure their recovery by filtration, or other means.

Crystallization of 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol (051810) Example 1 Crystallization from Ethyl Acetate/Hexane

1.25 g of prepurified (see U.S. Pat. No. 7,238,681) crude 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol was dissolved in ethyl acetate (3 ml) at room temperature and hexane (300 ml) was poured into the vigorously shaken solution. The mixture was kept in a refrigerator (at 4° C.) overnight and the resulted crystals were filtered off, washed with one portion (30 ml) of cooled (4° C.) hexane and dried under reduced pressure for 3 h giving 1.10 g of a pure product.

In order to obtain crystals acceptable for the X-ray experiment, 1α-Hydroxy-2-methylene-18,19-dinor-homopregnacalciferol (12 mg) was placed in an inner tube of a vessel and dissolved in 300 μl of benzene. To an outer tube of the vessel hexane (2 ml) was poured so that a benzene to hexane ratio of about 13:87, by volume, is obtained, and the whole system was carefully purged with argon, and then maintained as a closed system. The vessel was kept tightly closed for 4 days at room temperature. Crystals were grown employing diffusive exchange of the two solvents.

A colorless rod-shaped crystal of dimensions 0.73×0.08×0.02 mm was selected for structural analysis. Intensity data were collected using a Bruker AXS Platinum 135 CCD detector controlled with the PROTEUM software suite (Bruker AXS Inc., Madison, Wis.). The x-ray source was CuKα radiation (1.54178 Å) from a Rigaku RU200 x-ray generator equipped with Montel optics, operated at 50 kV and 90 mA. The x-ray data were processed with SAINT version 7.06 Å (Bruker AXS Inc.) and internally scaled with SADABS version 2005/1 (Bruker AXS Inc.). The sample was mounted on a glass fiber using vacuum grease and cooled to 100 K. The intensity data were measured as a series of phi and omega oscillation frames each of 10 for 60-120 sec/frame. The detector was operated in 1024×1024 mode and was positioned 5.0 cm from the sample. Cell parameters were determined from a non-linear least squares fit of 9999 peaks in the range of 3.0<theta<50.80. The data were merged to form a set of 4693 independent data with R(int)=0.0884.

The orthorhombic space group P2(1)2(1)2(1) was determined by systematic absences and statistical tests and verified by subsequent refinement. The structure was solved by direct methods and refined by full-matrix least-squares methods on F², (a) G. M. Sheldrick (1994), SHELXTL Version 5 Reference Manual, Bruker AXS Inc.; (b) International Tables for Crystallography, Vol. C, Kluwer: Boston (1995). The asymmetric unit is comprised of two molecules of 051810 and a benzene molecule. Molecule “A” is shown in FIG. 1, with thermal ellipsoids drawn at the 40% probability level. Based on lattice packing, the benzene molecule could not be present at full occupancy, and refinement of its occupancy led to a value of approximately 0.5. The presence of the benzene molecule lead to a disorder in a portion of molecule “B”. Refinement of the occupancies of the two disordered configurations independently of the occupancy of the benzene converged also at a value of about 0.5 for each. FIG. 2 a shows molecule B in its configuration in the absence of the benzene molecule, and FIG. 2 b shows its configuration in the presence of the benzene molecule; both figures are drawn with thermal ellipsoids at the 40% probability level. FIG. 3 shows a ball-and-stick representation of the entire asymmetric unit, with the hollow bonds showing the conformation in the presence of the benzene molecule. Hydrogen atom positions were refined by a riding model with idealized geometry. Non-hydrogen atoms were refined with anisotropic displacement parameters. The benzene molecule was refined with idealized geometry. A total of 559 parameters were refined against 26 restraints and 4693 data to give wR2=0.2524 and S=0.951 for weights of w=1/[s²(F²)+(0.1719P)²], where P=[F_(o) ²+2F_(c) ²]/3. The final R(F) was 0.0910 for the 6781 observed data. The largest shift/s.u. was 0.001 in the final refinement cycle and the final difference map had maxima and minima of 0.366 and −0.305 e/Å³, respectively. The absolute structure was determined by refinement of the Flack parameter, H. D. Flack, Acta Cryst. A, vol. 39, 876-881 (1983).

The three dimensional structure of 051810 as defined by the following physical data and atomic positional parameters described and calculated herein is illustrated in FIGS. 1, 2 a, 2 b and 3.

TABLE 1 Crystal data and structure refinement for 051810. Identification Code 051810 Empirical formula C45 H67 O4 Formula weight 671.99 Temperature 100(1) K Wavelength 1.54178 Å Crystal system Orthorhombic Space group P2(1)2(1)2(1) Unit cell dimensions a = 4.8020(10) Å α = 90° b = 22.940(5) Å β = 90° c = 36.124(7) Å γ = 90° Volume 3979.3(14) Å³ Z 4 Density (calculated) 1.122 Mg/m³ Absorption coefficient 0.533 mm⁻¹ F(000) 1476 Crystal 0.73 × 0.08 × 0.02 mm Theta range for data collection 2.28 to 54.17° Limiting indices −4 < h < 4, −24 < k < 23, −37 < 1 < 37 Reflections collected 12592 Independent reflections 4693 [R(int) = 0.0884] Completeness to Theta = 54.17° 98.2% Refinement method Full-matrix least-squares on F² Data/restraints/parameters 4693/26/559 Goodness-of-fit on F² 0.951 Final R indices [I > 2σ(I)] R1 = 0.0910, wR2 = 0.2214 R indices (all data) R1 = 0.1268, wR2 = 0.2524 Extinction coefficient 0.0124(12) Largest diff. peak and hole 0.366 and −0.305 e/A³ Melting Point 140-145° C.

TABLE 2 Atomic coordinates (× 10⁴) and equivalent isotropic displacement parameters (Å × 10³] for 051810. U(eq) is defined as one third of the trace of the orthogonalized U_(ij) tensor. X y z U(eq) O(1A)  −322(12)  7615(2) 6913(2)  59(2) O(3A) −2739(11)  9404(2) 7179(1)  51(1) C(10A)  −165(18)  8424(3) 6486(2)  47(2) C(1A)  −994(17)  8232(3) 6868(2)  46(2) C(3A)    148(16)  9249(3) 7108(2)  49(2) C(14A) −7331(19)  8940(3) 5377(2)  48(2) C(4A)    864(18)  9437(3) 6719(2)  49(2) C(13A) −6378(17)  9119(3) 4990(2)  42(2) C(7A) −4130(18)  9025(3) 5916(2)  50(2) C(17A) −7691(17)  8673(3) 4726(2)  47(2) C(2A)    472(16)  8595(3) 7156(2)  47(2) C(15A) −7129(18)  8276(3) 5360(2)  49(2) C(8A) −5795(16)  9274(3) 5667(2)  43(2) C(9A) −6387(19)  9924(3) 5624(2)  52(2) C(12A) −7120(18)  9770(3) 4931(2)  46(2) C(5A)  −649(16)  9072(3) 6439(2)  43(2) C(16A) −8423(18)  8158(3) 4986(2)  50(2) C(21A) −4792(18)  9008(3) 4177(2)  48(2) C(20A) −5793(17)  8486(3) 4408(2)  45(2) C(11A) −5708(19) 10137(3) 5234(2)  51(2) C(6A) −2416(17)  9326(3) 6193(2)  47(2) C(22A) −7262(18)  8050(3) 4144(2)  55(2) C(2A′)   1940(20)  8381(4) 7432(2)  76(3) O(3B) −3150(11) 10326(2) 7677(1)  48(1) O(1B) −4693(10) 12069(2) 8071(1)  40(1) C(1B) −4362(16) 11592(3) 7816(2)  39(2) C(2B) −6068(16) 11074(3) 7930(2)  40(2) C(10B) −5147(19) 11778(3) 7423(2)  49(2) C(3B) −5950(17) 10575(3) 7667(2)  46(2) C(4B) −6576(18) 10759(3) 7270(2)  48(2) C(6B) −3204(17) 11254(3) 6861(2)  51(2) C(5B) −4833(17) 11275(3) 7155(2)  44(2) C(7B) −1376(17) 11745(4) 6734(2)  58(2) C(2B) −7707(19) 11071(3) 8221(2)  56(2) C(8B)    259(18) 11713(5) 6435(3)  75(3) C(12B)   2040(50) 12137(10) 5703(5) 105(13) C(9B)    720(60) 11337(11) 6171(5)  65(7) C(14B)   1730(40) 12297(7) 6369(5)  66(5) C(13B)   1580(50) 12609(9) 5997(5)  86(8) C(11B)    420(50) 11584(11) 5782(5)  96(11) C(15B)   1870(60) 12851(8) 6602(7) 111(14) C(17B)   3160(40) 13190(9) 5995(8) 109(12) C(16B)   3350(40) 13356(9) 6404(7) 101(9) C(20B)   2050(50) 13662(10) 5735(7) 151(15) C(22B)   3890(50) 14206(10) 5741(8) 185(18) C(21B)   1610(120) 13442(14) 5339(8) 230(30) C(12′)   1350(40) 11726(7) 5609(6)  45(6) C(9′)    160(70) 11067(10) 6145(6)  46(8) C(14′)   2290(40) 12120(8) 6246(4)  45(8) C(13′)   1240(50) 12265(7) 5860(4)  36(6) C(11′)  −560(50) 11251(8) 5752(5)  39(6) C(15′)   2350(40) 12687(8) 6459(5)  33(5) C(17′)   2980(40) 12809(6) 5789(4)  38(5) C(16′)   3750(40) 13067(7) 6167(4)  35(6) C(20′)   1650(50) 13270(7) 5543(5)  72(8) C(22′)   3670(70) 13750(10) 5428(8)  78(9) C(21′)    80(60) 13041(10) 5206(6)  76(9) C(1)   1350(20) 14678(5) 6378(3)  67(5) C(2)   1060(20) 14340(5) 6695(4)  64(5) C(3)   3410(30) 14137(4) 6879(2)  69(5) C(4)   6050(20) 14270(4) 6746(3)  58(5) C(5)   6340(20) 14608(4) 6429(3)  62(5) C(6)   3990(30) 14811(4) 6245(3)  74(6)

TABLE 3 Bond lengths [Å] for 051810. O(1A)—C(1A) 1.460(8) O(1A)—H(1AA) 0.8200 O(3A)—C(3A) 1.454(9) O(3A)—H(3AA) 0.8200 C(10A)—C(1A) 1.502(9) C(10A)—C(5A) 1.513(10) C(10A)—H(10A) 0.9700 C(10A)—H(10B) 0.9700 C(1A)—C(2A) 1.508(11) C(1A)—H(1AB) 0.9800 C(3A)—C(4A) 1.507(10) C(3A)—C(2A) 1.518(10) C(3A)—H(3AB) 0.9800 C(14A)—C(8A) 1.492(10) C(14A)—C(13A) 1.527(10) C(14A)—C(15A) 1.529(9) C(14A)—H(14A) 0.9800 C(4A)—C(5A) 1.501(10) C(4A)—H(4AA) 0.9700 C(4A)—H(4AB) 0.9700 C(13A)—C(17A) 1.534(10) C(13A)—C(12A) 1.550(9) C(13A)—H(13A) 0.9800 C(7A)—C(8A) 1.332(10) C(7A)—C(6A) 1.469(10) C(7A)—H(7AA) 0.9300 C(17A)—C(20A) 1.529(10) C(17A)—C(16A) 1.548(10) C(17A)—H(17A) 0.9800 C(2A)—C(2A′) 1.314(11) C(15A)—C(16A) 1.511(10) C(15A)—H(15A) 0.9700 C(15A)—H(15B) 0.9700 C(8A)—C(9A) 1.526(10) C(9A)—C(11A) 1.528(9) C(9A)—H(9AA) 0.9700 C(9A)—H(9AB) 0.9700 C(12A)—C(11A) 1.538(10) C(12A)—H(12A) 0.9700 C(12A)—H(12B) 0.9700 C(5A)—C(6A) 1.359(10) C(16A)—H(16A) 0.9700 C(16A)—H(16B) 0.9700 C(21A)—C(20A) 1.536(10) C(21A)—H(21A) 0.9600 C(21A)—H(21B) 0.9600 C(21A)—H(21C) 0.9600 C(20A)—C(22A) 1.552(10) C(20A)—H(20A) 0.9800 C(11A)—H(11A) 0.9700 C(11A)—H(118) 0.9700 C(6A)—H(6AA) 0.9300 C(22A)—H(22A) 0.9600 C(22A)—H(22B) 0.9600 C(22A)—H(22C) 0.9600 C(2A′)—H(1A′) 0.9300 C(2A′)—H(2A′) 0.9300 O(3B)—C(3B) 1.461(10) O(3B)—H(3BA) 0.8200 O(1B)—C(1B) 1.439(8) O(1B)—H(1BA) 0.8200 C(1B)—C(2B) 1.501(10) C(1B)—C(10B) 1.532(9) C(1B)—H(1BB) 0.9800 C(2B)—C(2B′) 1.313(10) C(2B)—C(3B) 1.488(10) C(10B)—C(5B) 1.514(9) C(10B)—H(10C) 0.9700 C(10B)—H(10D) 0.9700 C(3B)—C(4B) 1.526(7) C(3B)—H(3BB) 0.9800 C(4B)—C(5B) 1.506(10) C(4B)—H(4BA) 0.9700 C(4B)—H(4BB) 0.9700 C(6B)—C(5B) 1.321(10) C(6B)—C(7B) 1.499(8) C(6B)—H(6BA) 0.9300 C(7B)—C(8B) 1.338(12) C(7B)—H(7BA) 0.9300 C(2B′)—H(1B′) 0.9300 C(2B′)—H(2B′) 0.9300 C(8B)—C(9B) 1.50(2) C(8B)—C(14′) 1.514(10) C(8B)—C(14B) 1.534(10) C(8B)—C(9′) 1.52(2) C(12B)—C(11B) 1.516(10) C(12B)—C(13B) 1.534(10) C(12B)—H(12C) 0.9700 C(12B)—H(12D) 0.9700 C(9B)—C(11B) 1.522(10) C(9B)—H(9BA) 0.9700 C(9B)—H(9BB) 0.9700 C(14B)—C(15B) 1.527(10) C(14B)—C(13B) 1.524(10) C(14B)—H(14B) 0.9800 C(13B)—C(17B) 1.532(10) C(13B)—H(13B) 0.9800 C(11B)—H(11C) 0.9700 C(11B)—H(11D) 0.9700 C(15B)—C(16B) 1.535(10) C(15B)—H(15C) 0.9700 C(15B)—H(15D) 0.9700 C(17B)—C(16B) 1.528(10) C(17B)—C(20B) 1.528(10) C(17B)—H(17B) 0.9800 C(16B)—H(16C) 0.9700 C(16B)—H(16D) 0.9700 C(20B)—C(22B) 1.528(10) C(20B)—C(21B) 1.532(11) C(20B)—H(20B) 0.9800 C(22B)—H(22D) 0.9600 C(22B)—H(22E) 0.9600 C(22B)—H(22F) 0.9600 C(21B)—H(21D) 0.9600 C(21B)—H(21E) 0.9600 C(21B)—H(21F) 0.9600 C(12′)—C(11′) 1.513(10) C(12′)—C(13′) 1.534(10) C(12′)—H(12E) 0.9700 C(12′)—H(12F) 0.9700 C(9′)—C(11′) 1.519(10) C(9′)—H(9BC) 0.9700 C(9′)—H(9BD) 0.9700 C(14′)—C(15′) 1.512(10) C(14′)—C(13′) 1.517(10) C(14′)—H(14′) 0.9800 C(13′)—C(17′) 1.523(10) C(13′)—H(13′) 0.9800 C(11′)—H(11E) 0.9700 C(11′)—H(11F) 0.9700 C(15′)—C(16′) 1.524(10) C(15′)—H(15E) 0.9700 C(15′)—H(15F) 0.9700 C(17′)—C(20′) 1.523(10) C(17′)—C(16′) 1.533(10) C(17′)—H(17′) 0.9800 C(16′)—H(16E) 0.9700 C(16′)—H(16F) 0.9700 C(20′)—C(21′) 1.525(10) C(20′)—C(22′) 1.528(10) C(20′)—H(20C) 0.9800 C(22′)—H(22G) 0.9600 C(22′)—H(22H) 0.9600 C(22′)—H(22I) 0.9600 C(21′)—H(21G) 0.9600 C(21′)—H(21H) 0.9600 C(21′)—H(21I) 0.9600 C(1)—C(2) 1.3900 C(1)—C(6) 1.3900 C(1)—H(1A) 0.9300 C(2)—C(3) 1.3900 C(2)—H(2A) 0.9300 C(3)—C(4) 1.3900 C(3)—H(3A) 0.9300 C(4)—C(5) 1.3900 C(4)—H(4A) 0.9300 C(5)—C(6) 1.3900 C(5)—H(5A) 0.9300 C(6)—H6A) 0.9300

TABLE 4 Bond angles [°] for 051810. C(1A)—O(1A)—H(1AA) 109.5 C(3A)—O(3A)—H(3AA) 109.5 C(1A)—C(10A)—C(5A) 110.6(6) C(1A)—C(10A)—H(10A) 109.7 C(5A)—C(10A)—H(10A) 109.6 C(1A)—C(10A)—H(10B) 109.4 C(5A)—C(10A)—H(10B) 109.4 H(10A)—C(10A)—H(10B) 108.1 O(1A)—C(1A)—C(10A) 109.1(6) O(1A)—C(1A)—C(2A) 110.9(6) C(10A)—C(1A)—C(2A) 110.4(6) O(1A)—C(1A)—H(1AB) 108.8 C(10A)—C(1A)—H(1AB) 108.8 C(2A)—C(1A)—H(1AB) 108.8 O(3A)—C(3A)—C(4A) 108.2(6) O(3A)—C(3A)—C(2A) 108.6(6) C(4A)—C(3A)—C(2A) 111.5(6) O(3A)—C(3A)—H(3AB) 109.5 C(4A)—C(3A)—H(3AB) 109.5 C(2A)—C(3A)—H(3AB) 109.5 C(8A)—C(14A)—C(13A) 110.9(7) C(8A)—C(14A)—C(15A) 120.6(7) C(13A)—C(14A)—C(15A) 102.2(6) C(8A)—C(14A)—H(14A) 107.5 C(13A)—C(14A)—H(14A) 107.5 C(15A)—C(14A)—H(14A) 107.6 C(5A)—C(4A)—C(3A) 111.0(6) C(5A)—C(4A)—H(4AA) 109.4 C(3A)—C(4A)—H(4AA) 109.4 C(5A)—C(4A)—H(4AB) 109.4 C(3A)—C(4A)—H(4AB) 109.5 H(4AA)—C(4A)—H(4AB) 108.0 C(14A)—C(13A)—C(17A) 105.5(6) C(14A)—C(13A)—C(12A) 108.4(6) C(17A)—C(13A)—C(12A) 117.6(6) C(14A)—C(13A)—H(13A) 108.4 C(17A)—C(13A)—H(13A) 108.3 C(12A)—C(13A)—H(13A) 108.4 C(8A)—C(7A)—C(6A) 126.6(7) C(8A)—C(7A)—H(7AA) 116.8 C(6A)—C(7A)—H(7AA) 116.6 C(20A)—C(17A)—C(13A) 114.2(7) C(20A)—C(17A)—C(16A) 112.1(6) C(13A)—C(17A)—C(16A) 103.1(5) C(20A)—C(17A)—H(17A) 109.1 C(13A)—C(17A)—H(17A) 109.1 C(16A)—C(17A)—H(17A) 109.1 C(2A′)—C(2A)—C(1A) 124.4(7) C(2A′)—C(2A)—C(3A) 120.9(8) C(1A)—C(2A)—C(3A) 114.7(6) C(16A)—C(15A)—C(14A) 100.9(6) C(16A)—C(15A)—H(15A) 111.6 C(14A)—C(15A)—H(15A) 111.6 C(16A)—C(15A)—H(15B) 111.6 C(14A)—C(15A)—H(15B) 111.5 H(15A)—C(15A)—H(15B) 109.4 C(7A)—C(8A)—C(14A) 123.4(6) C(7A)—C(8A)—C(9A) 126.8(7) C(14A)—C(8A)—C(9A) 109.8(6) C(11A)—C(9A)—C(8A) 111.5(6) C(11A)—C(9A)—H(9AA) 109.3 C(8A)—C(9A)—H(9AA) 109.4 C(11A)—C(9A)—H(9AB) 109.3 C(8A)—C(9A)—H(9AB) 109.4 H(9AA)—C(9A)—H(9AB) 108.0 C(11A)—C(12A)—C(13A) 109.2(6) C(11A)—C(12A)—H(12A) 109.8 C(13A)—C(12A)—H(12A) 109.8 C(11A)—C(12A)—H(12B) 109.9 C(13A)—C(12A)—H(12B) 109.8 H(12A)—C(12A)—H(12B) 108.3 C(6A)—C(5A)—C(4A) 120.2(6) C(6A)—C(5A)—C(10A) 126.2(7) C(4A)—C(5A)—C(10A) 113.4(6) C(15A)—C(16A)—C(17A) 108.1(6) C(15A)—C(16A)—H(16A) 110.1 C(17A)—C(16A)—H(16A) 110.1 C(15A)—C(16A)—H(16B) 110.0 C(17A)—C(16A)—H(16B) 110.1 H(16A)—C(16A)—H(16B) 108.4 C(20A)—C(21A)—H(21A) 109.6 C(20A)—C(21A)—H(21B) 109.4 H(21A)—C(21A)—H(21B) 109.5 C(20A)—C(21A)—H(21C) 109.4 H(21A)—C(21A)—H(21C) 109.5 H(21B)—C(21A)—H(21C) 109.5 C(17A)—C(20A)—C(21A) 112.2(6) C(17A)—C(20A)—C(22A) 111.9(7) C(21A)—C(20A)—C(22A) 108.1(6) C(17A)—C(20A)—H(20A) 108.2 C(21A)—C(20A)—H(20A) 108.2 C(22A)—C(20A)—H(20A) 108.2 C(9A)—C(11A)—C(12A) 112.8(7) C(9A)—C(11A)—H(11A) 109.0 C(12A)—C(11A)—H(11A) 109.0 C(9A)—C(11A)—H(11B) 109.1 C(12A)—C(11A)—H(11B) 109.0 H(11A)—C(11A)—H(11B) 107.8 C(5A)—C(6A)—C(7A) 126.5(7) C(5A)—C(6A)—H(6AA) 116.8 C(7A)—C(6A)—H(6AA) 116.7 C(20A)—C(22A)—H(22A) 109.4 C(20A)—C(22A)—H(22B) 109.5 H(22A)—C(22A)—H(22B) 109.5 C(20A)—C(22A)—H(22C) 109.5 H(22A)—C(22A)—H(22C) 109.5 H(22B)—C(22A)—H(22C) 109.5 C(2A)—C(2A′)—H(1A′) 120.0 C(2A)—C(2A′)—H(2A′) 120.0 H(1A′)—C(2A′)—H(2A′) 120.0 C(3B)—O(3B)—H(3BA) 109.4 C(1B)—O(1B)—H(1BA) 109.4 O(1B)—C(1B)—C(2B) 111.5(5) O(1B)—C(1B)—C(10B) 110.7(5) C(2B)—C(1B)—C(10B) 110.0(6) O(1B)—C(1B)—H(1BB) 108.2 C(2B)—C(1B)—H(1BB) 108.2 C(10B)—C(1B)—H(1BB) 108.2 C(2B′)—C(2B)—C(3B) 122.1(7) C(2B′)—C(2B)—C(1B) 123.4(7) C(3B)—C(2B)—C(1B) 114.4(6) C(5B)—C(10B)—C(1B) 110.8(6) C(5B)—C(10B)—H(10C) 109.6 C(1B)—C(10B)—H(10C) 109.5 C(5B)—C(10B)—H(10D) 109.4 C(1B)—C(10B)—H(10D) 109.5 H(10C)—C(10B)—H(10D) 108.1 O(3B)—C(3B)—C(2B) 108.7(6) O(3B)—C(3B)—C(4B) 108.2(6) C(2B)—C(3B)—C(4B) 112.4(6) O(3B)—C(3B)—H(3BB) 109.1 C(2B)—C(3B)—H(3BB) 109.2 C(4B)—C(3B)—H(3BB) 109.2 C(5B)—C(4B)—C(3B) 111.5(6) C(5B)—C(4B)—H(4BA) 109.3 C(3B)—C(4B)—H(4BA) 109.2 C(5B)—C(4B)—H(4BB) 109.4 C(3B)—C(4B)—H(4BB) 109.4 H(4BA)—C(4B)—H(4BB) 108.0 C(5B)—C(6B)—C(7B) 124.5(7) C(5B)—C(6B)—H(6BA) 117.8 C(7B)—C(6B)—H(6BA) 117.7 C(6B)—C(5B)—C(4B) 121.5(6) C(6B)—C(5B)—C(10B) 126.9(7) C(4B)—C(5B)—C(10B) 111.6(6) C(8B)—C(7B)—C(6B) 123.3(8) C(8B)—C(7B)—H(7BA) 118.3 C(6B)—C(7B)—H(7BA) 118.4 C(2B)—C(2B′)—H(1B′) 120.1 C(2B)—C(2B′)—H(2B′) 119.9 H(1B′)—C(2B′)—H(2B′) 120.0 C(9B)—C(8B)—C(7B) 136.7(13) C(9B)—C(8B)—C(14′)  88.1(14) C(7B)—C(8B)—C(14′) 135.1(12) C(9B)—C(8B)—C(14B) 112.6(15) C(7B)—C(8B)—C(14B) 110.4(11) C(14′)—C(8B)—C(14B)  24.9(8) C(9B)—C(8B)—C(9′)  16.9(16) C(7B)—C(8B)—C(9′) 119.8(12) C(14′)—C(8B)—C(9′) 105.0(13) C(14B)—C(8B)—C(9′) 129.4(13) C(11B)—C(12B)—C(13B) 112.7(18) C(11B)—C(12B)—H(12C) 108.9 C(13B)—C(12B)—H(12C) 108.6 C(11B)—C(12B)—H(12D) 109.3 C(13B)—C(12B)—H(12D) 109.5 H(12C)—C(12B)—H(12D) 107.8 C(8B)—C(9B)—C(11B) 114.4(19) C(8B)—C(9B)—H(9BA) 109.1 C(11B)—C(9B)—H(9BA) 108.4 C(8B)—C(9B)—H(9BB) 108.6 C(11B)—C(9B)—H(9BB) 108.6 H(9BA)—C(9B)—H(9BB) 107.6 C(15B)—C(14B)—C(13B)  95.5(15) C(15B)—C(14B)—C(8B) 131.5(13) C(13B)—C(14B)—C(8B) 121.8(14) C(15B)—C(14B)—H(14B) 100.6 C(13B)—C(14B)—H(14B) 101.3 C(8B)—C(14B)—H(14B) 101.0 C(14B)—C(13B)—C(17B) 113.0(14) C(14B)—C(13B)—C(12B) 105.8(15) C(17B)—C(13B)—C(12B) 122.6(18) C(14B)—C(13B)—H(13B) 104.3 C(17B)—C(13B)—H(13B) 104.4 C(12B)—C(13B)—H(13B) 105.0 C(12B)—C(11B)—C(9B) 115.9(19) C(12B)—C(11B)—H(11C) 108.0 C(9B)—C(11B)—H(11C) 108.5 C(12B)—C(11B)—H(11D) 108.5 C(9B)—C(11B)—H(11D) 108.3 H(11)—C(11B)—H(11D) 107.4 C(14B)—C(15B)—C(16B) 113.1(17) C(14B)—C(15B)—H(15C) 109.4 C(16B)—C(15B)—H(15C) 109.8 C(14B)—C(15B)—H(15D) 107.9 C(16B)—C(15B)—H(15D) 108.7 H(15C)—C(15B)—H(15D) 107.6 C(16B)—C(17B)—C(20B) 115.9(19) C(16B)—C(17B)—C(13B) 104.0(16) C(20B)—C(17B)—C(13B) 116.6(16) C(16B)—C(17B)—H(17B) 106.2 C(20B)—C(17B)—H(17B) 106.6 C(13B)—C(17B)—H(17B) 106.7 C(17B)—C(16B)—C(15B) 103.5(18) C(17B)—C(16B)—H(16C) 111.1 C(15B)—C(16B)—H(16C) 110.8 C(17B)—C(16B)—H(16D) 111.7 C(15B)—C(16B)—H(16D) 110.5 H(16C)—C(16B)—H(16D) 109.2 C(22B)—C(20B)—C(17B) 111.7(17) C(22B)—C(20B)—C(21B) 111(2) C(17B)—C(20B)—C(21B) 113(2) C(22B)—C(20B)—H(20B) 107.2 C(17B)—C(20B)—H(20B) 107.2 C(21B)—C(20B)—H(20B) 106.3 C(20B)—C(22B)—H(22D) 109.5 C(20B)—C(22B)—H(22E) 109.5 H(22D)—C(22B)—H(22E) 109.5 C(20B)—C(22B)—H(22F) 109.3 H(22D)—C(22B)—H(22F) 109.5 H(22E)—C(22B)—H(22F) 109.5 C(20B)—C(21B)—H(21D) 110.2 C(20B)—C(21B)—H(21E) 109.4 H(21D)—C(21B)—H(21E) 109.5 C(20B)—C(21B)—H(21F) 108.8 H(21D)—C(21B)—H(21F) 109.5 H(21E)—C(21B)—H(21F) 109.5 C(11′)—C(12′)—C(13′) 111.0(13) C(11′)—C(12′)—H(12E) 109.4 C(13′)—C(12′)—H(12E) 109.7 C(11′)—C(12′)—H(12F) 109.8 C(13′)—C(12′)—H(12F) 108.9 H(12E)—C(12′)—H(12F) 108.0 C(11′)—C(9′)—C(8B) 108.5(15) C(11′)—C(9′)—H(9BC) 110.2 C(8B)—C(9′)—H(9BC) 109.7 C(11′)—C(9′)—H(9BD) 109.9 C(8B)—C(9′)—H(9BD) 110.3 H(9BC)—C(9′)—H(9BD) 108.3 C(8B)—C(14′)—C(15′) 108.3(13) C(8B)—C(14′)—C(13′) 109.7(13) C(15′)—C(14′)—C(13′) 106.5(15) C(8B)—C(14′)—H(14′) 111.1 C(15′)—C(14′)—H(14′) 110.6 C(13′)—C(14′)—H(14′) 110.5 C(14′)—C(13′)—C(17′)  98.8(11) C(14′)—C(13′)—C(12′) 110.8(17) C(17′)—C(13′)—C(12′) 122.8(15) C(14′)—C(13′)—H(13′) 107.9 C(17′)—C(13′)—H(13′) 107.7 C(12′)—C(13′)—H(13′) 107.8 C(12′)—C(11′)—C(9′) 112.5(18) C(12′)—C(11′)—H(11E) 108.6 C(9′)—C(11′)—H(11E) 108.7 C(12′)—C(11′)—H(11F) 109.6 C(9′)—C(11′)—H(11F) 109.5 H(11E)—C(11′)—H(11F) 107.9 C(14′)—C(15′)—C(16′)  98.5(12) C(14′)—C(15′)—H(15E) 112.0 C(16′)—C(15′)—H(15E) 112.7 C(14′)—C(15′)—H(15F) 111.7 C(16′)—C(15′)—H(15F) 111.9 H(15E)—C(15′)—H(15F) 109.7 C(20′)—C(17′)—C(13′) 115.8(13) C(20′)—C(17′)—C(16′) 110.6(13) C(13′)—C(17′)—C(16′) 107.3(13) C(20′)—C(17′)—H(17′) 107.9 C(13′)—C(17′)—H(17′) 107.4 C(16′)—C(17′)—H(17′) 107.5 C(15′)—C(16′)—C(17′) 106.8(14) C(15′)—C(16′)—H(16E) 109.9 C(17′)—C(16′)—H(16E) 110.7 C(15′)—C(16′)—H(16F) 110.1 C(17′)—C(16′)—H(16F) 110.8 H(16E)—C(16′)—H(16F) 108.6 C(17′)—C(20′)—C(21′) 115.7(14) C(17′)—C(20′)—C(22′) 112.9(18) C(21′)—C(20′)—C(22′) 110(2) C(17′)—C(20′)—H(20C) 105.6 C(21′)—C(20′)—H(20C) 105.5 C(22′)—C(20′)—H(20C) 105.8 C(20′)—C(22′)—H(22G) 109.6 C(20′)—C(22′)—H(22H) 109.7 H(22G)—C(22′)—H(22H) 109.5 C(20′)—C(22′)—H(22I) 109.1 H(22G)—C(22′)—H(22I) 109.5 H(22H)—C(22′)—H(22I) 109.5 C(20′)—C(21′)—H(21G) 109.3 C(20′)—C(21′)—H(21H) 109.7 H(21G)—C(21′)—H(21H) 109.5 C(20′)—C(21′)—H(21I) 109.5 H(21G)—C(21′)—H(21I) 109.5 H(21H)—C(21′)—H(21I) 109.5 C(2)—C(1)—C(6) 120.0 C(2)—C(1)—H(1A) 120.0 C(6)—C(1)—H(1A) 120.0 C(1)—C(2)—C(3) 120.0 C(1)—C(2)—H(2A) 120.0 C(3)—C(2)—H(2A) 120.0 C(2)—C(3)—C(4) 120.0 C(2)—C(3)—H(3A) 120.0 C(4)—C(3)—H(3A) 120.0 C(5)—C(4)—C(3) 120.0 C(5)—C(4)—H(4A) 120.0 C(3)—C(4)—H(4A) 120.0 C(4)—C(5)—C(6) 120.00(5) C(4)—C(5)—H(5A) 120.0 C(6)—C(5)—H(5A) 120.0 C(5)—C(6)—C(1) 120.0 C(5)—C(6)—H(6A) 120.0 C(1)—C(6)—H(6A) 120.0

TABLE 5 Anisotropic displacement parameters [Å² × 10³] for 051810. The anisotropic displacement factor exponent takes the form: −2π² [h²a*²U₁₁ + . . . + 2hka*b*U₁₂] U₁₁ U₂₂ U₃₃ U₂₃ U₁₃ U₁₂ O (1A) 50 (4) 34 (3) 93 (4) 21 (3) 2 (3) 9 (3) O (3A) 41 (4) 48 (3) 64 (3) −2 (3) 7 (3) 6 (3) C (10A) 53 (6) 33 (4) 54 (5) −5 (3) −2 (4) −4 (4) C (1A) 35 (5) 27 (4) 76 (5) 12 (4) 3 (4) 5 (3) C (3A) 37 (5) 36 (4) 75 (5) −2 (4) −6 (4) 4 (4) C (14A) 53 (6) 36 (4) 56 (5) 3 (4) 0 (4) 6 (4) C (4A) 50 (6) 36 (4) 61 (5) 7 (4) 0 (4) −6 (4) C (13A) 42 (5) 35 (4) 50 (4) 8 (3) 4 (4) 9 (4) C (7A) 60 (6) 35 (4) 55 (5) −8 (4) 13 (4) −9 (4) C (17A) 42 (5) 45 (4) 52 (5) 7 (4) −3 (4) 3 (4) C (2A) 41 (5) 50 (5) 50 (4) 12 (4) 8 (4) 4 (4) C (15A) 52 (6) 39 (4) 58 (5) 8 (4) 6 (4) 0 (4) C (8A) 44 (5) 35 (4) 50 (5) 8 (4) 4 (4) 6 (4) C (9A) 53 (6) 47 (5) 56 (5) 2 (4) 10 (4) 1 (4) C (12A) 54 (6) 36 (4) 46 (4) 6 (3) 2 (4) 9 (4) C (5A) 36 (5) 39 (4) 55 (4) 0 (4) 4 (4) 1 (4) C (16A) 43 (5) 44 (5) 62 (5) 4 (4) −3 (4) 2 (4) C (21A) 48 (6) 43 (4) 53 (4) 1 (4) 2 (4) 10 (4) C (20A) 39 (5) 38 (4) 57 (5) 1 (4) −1 (4) 4 (4) C (11A) 59 (6) 40 (4) 53 (5) 4 (4) 3 (4) 5 (4) C (6A) 50 (5) 33 (4) 60 (5) 2 (4) 8 (4) −3 (4) C (22A) 59 (6) 47 (5) 59 (5) 0 (4) −12 (4) −1 (4) C (2A′) 77 (8) 78 (6) 74 (6) −4 (5) −5 (5) 33 (6) O (3B) 49 (4) 34 (3) 60 (3) −1 (2) −3 (3) 4 (2) O (1B) 48 (3) 31 (3) 41 (3) −5 (2) −3 (2) 4 (2) C (1B) 44 (5) 28 (4) 45 (4) −2 (3) −1 (3) −4 (3) C (2B) 37 (5) 42 (4) 41 (4) −3 (3) 0 (3) −4 (3) C (10B) 54 (6) 38 (4) 56 (5) −3 (4) 3 (4) −3 (4) C (3B) 49 (5) 32 (4) 57 (5) −6 (4) 0 (4) −3 (4) C (4B) 49 (5) 39 (4) 55 (5) −10 (4) 3 (4) −2 (4) C (6B) 49 (6) 55 (5) 48 (5) −6 (4) −4 (4) 10 (4) C (5B) 45 (5) 36 (4) 51 (4) −10 (3) −3 (4) 10 (4) C (7B) 38 (5) 79 (6) 57 (5) 15 (4) 1 (4) 12 (5) C (2B′) 59 (6) 42 (5) 66 (5) −1 (4) 1 (5) 4 (4) C (8B) 33 (6) 124 (9) 68 (6) 37 (7) 6 (5) 28 (6) C (12B) 83 (18) 190 (30) 43 (14) 64 (16) 31 (12) 80 (20) C (9B) 43 (13) 100 (20) 48 (13) 5 (13) −7 (9) 8 (16) C (14B) 16 (11) 118 (13) 63 (11) 38 (10) 26 (8) 27 (10) C (13B) 74 (16) 109 (19) 74 (15) 40 (15) 38 (13) 44 (15) C (11B) 32 (16) 170 (40) 89 (19) 40 (20) 22 (12) 20 (17) C (15B) 44 (14) 140 (30) 150 (30) 110 (20) 30 (20) 20 (20) C (17B) 9 (12) 87 (19) 230 (30) 70 (20) −3 (15) 13 (11) C (16B) 50 (13) 84 (15) 170 (20) 66 (17) 0 (13) −1 (11) C (20B) 110 (20) 140 (30) 200 (30) 120 (30) 70 (20) 90 (20) C (22B) 120 (20) 140 (20) 300 (40) 140 (30) 130 (30) 51 (19) C (21B) 410 (90) 170 (50) 120 (30) 100 (40) 100 (50) 100 (50) C (12′) 44 (15) 10 (9) 82 (17) −11 (11) 3 (11) 0 (9) C (9′ ) 38 (17) 23 (13) 77 (17) −8 (11) −5 (11) −1 (10) C (14′) 18 (16) 64 (14) 53 (16) 17 (12) 35 (12) 35 (12) C (13′) 50 (16) 34 (14) 26 (13) −8 (9) 2 (11) 0 (12) C (11′) 34 (14) 42 (12) 41 (11) −8 (9) 0 (9) −22 (9) C (15′) 15 (13) 44 (9) 39 (10) 12 (7) 5 (7) −3 (8) C (17′) 44 (13) 13 (11) 56 (12) 2 (9) −7 (10) −4 (9) C (16′) 37 (14) 14 (10) 56 (13) −22 (10) −7 (11) 12 (9) C (20′) 130 (20) 48 (17) 42 (14) −7 (13) −1 (15) −9 (16) C (22′) 160 (30) 31 (13) 46 (14) 5 (11) 35 (15) −24 (14) C (21′) 120 (20) 49 (15) 56 (14) 18 (11) −35 (14) 9 (14) C (1) 55 (14) 51 (11) 95 (14) −8 (10) 2 (10) 11 (9) C (2) 62 (14) 50 (10) 80 (13) −31 (10) 15 (10) 9 (10) C (3) 83 (16) 53 (10) 71 (12) −10 (9) 12 (12) −1 (11) C (4) 63 (13) 36 (9) 74 (12) −12 (8) 3 (9) 4 (9) C (5) 91 (15) 30 (9) 67 (12) 7 (8) 7 (11) 3 (9) C (6) 87 (17) 49 (11) 85 (13) −1 (10) 7 (13) 11 (11)

TABLE 6 Hydrogen coordinates (× 10⁴) and isotropic displacement parameters (Å² × 10³) for 051810. x y z U(eq) H(1AA) −772 7508 7121 88 H(3AA) −3165 9304 7389 76 H(10A) −1247 8212 6304 56 H(10B) 1787 8337 6445 56 H(1AB) −3008 8283 6896 55 H(3AB) 1358 9452 7284 59 H(14A) −9307 9042 5399 58 H(4AA) 363 9843 6686 59 H(4AB) 2855 9400 6681 59 H(13A) −4349 9078 4977 51 H(7AA) −4044 8620 5914 60 H(17A) −9414 8836 4624 56 H(15A) −5210 8145 5369 59 H(15B) −8177 8093 5557 59 H(9AA) −8336 9998 5677 62 H(9AB) −5281 10140 5802 62 H(12A) −6487 9896 4689 55 H(12B) −9123 9821 4943 55 H(16A) −10428 8123 5010 60 H(16B) −7704 7797 4884 60 H(21A) −3850 9281 4334 72 H(21B) −6364 9194 4063 72 H(21C) −3535 8874 3988 72 H(20A) −4155 8293 4514 53 H(11A) −3707 10126 5198 61 H(11B) −6304 10539 5209 61 H(6AA) −2553 9730 6201 57 H(22A) −5981 7928 3955 82 H(22B) −8841 8235 4031 82 H(22C) −7870 7716 4282 82 H(1A′) 2123 7979 7458 114 H(2A′) 2789 8630 7600 114 H(3BA) −2777 10226 7889 72 H(1BA) −4248 11964 8280 60 H(1BB) −2397 11477 7816 47 H(10C) −7059 11915 7420 59 H(10D) −3958 12098 7346 59 H(3BB) −7298 10278 7744 55 H(4BA) −6208 10435 7105 57 H(4BB) −8532 10859 7249 57 H(6BA) −3190 10912 6723 61 H(7BA) −1379 12089 6870 69 H(1B′) −8841 10751 8268 84 H(2B′) −7733 11389 8381 84 H(12C) 1489 12288 5463 126 H(12D) 4012 12045 5691 126 H(9BA) −563 11014 6199 78 H(9BB) 2594 11184 6199 78 H(14B) 3687 12175 6372 79 H(13B) −381 12719 5970 103 H(11C) 1004 11288 5606 115 H(11D) −1538 11661 5737 155 H(15C) 2846 12767 6831 134 H(15D) −5 12972 6664 134 H(17B) 5058 13104 5913 131 H(16C) 2418 13724 6451 121 H(16D) 5278 13387 6482 121 H(20B) 220 13778 5830 181 H(22D) 3864 14386 5502 277 H(22E) 5760 14097 5804 277 H(22F) 3189 14475 5922 277 H(21D) −117 13593 5245 349 H(21E) 1547 13024 5339 349 H(21F) 3116 13572 5186 349 H(12E) 785 11834 5360 54 H(12F) 3241 11581 5598 54 H(9BC) 1963 10874 6148 55 H(9BD) −1223 10796 6237 55 H(14′) 4150 11946 6235 54 H(13′) −708 12386 5882 44 H(11E) −427 10915 5590 47 H(11F) −2464 11390 5746 47 H(15E) 3449 12658 6683 39 H(15F) 490 12824 6519 39 H(17′) 4716 12684 5669 45 H(16E) 5753 13064 6201 42 H(16F) 3094 13466 6185 42 H(20C) 240 13461 5697 87 H(22G) 2711 14036 5282 118 H(22H) 5163 13584 5286 118 H(22I) 4425 13933 5646 118 H(21G) −707 13362 5071 114 H(21H) −1382 12784 5285 114 H(21I) 1345 12832 5048 114 H(1A) −219 14814 6255 81 H(2A) −706 14251 6784 77 H(3A) 3213 13911 7091 83 H(4A) 7619 14134 6869 69 H(5A) 8105 14697 6340 75 H(6A) 4186 15037 6032 89

TABLE 7 Observed and calculated structure factors for 051810. h k l 10Fo 10Fc 10s 2 0 0 42 37 16 4 0 0 138 11 0 15 1 1 0 437 450 11 2 1 0 362 322 16 3 1 0 252 218 24 0 2 0 271 282 8 1 2 0 426 437 14 2 2 0 277 256 13 3 2 0 352 250 29 4 2 0 158 155 27 1 3 0 177 158 10 2 3 0 400 366 25 3 3 0 502 441 19 4 3 0 108 115 41 0 4 0 2471 1827 86 1 4 0 364 399 10 2 4 0 337 336 22 3 4 0 262 232 10 4 4 0 121 91 37 1 5 0 76 86 7 2 5 0 79 85 29 3 5 0 117 101 12 4 5 0 175 222 27 0 6 0 296 309 14 1 6 0 589 676 20 2 6 0 86 46 29 3 6 0 199 199 14 1 7 0 111 130 6 2 7 0 99 12 27 3 7 0 164 132 10 0 8 0 833 923 65 1 8 0 272 335 26 2 8 0 75 86 41 3 8 0 158 156 23 1 9 0 300 305 18 2 9 0 293 277 14 3 9 0 306 302 16 0 10 0 259 184 39 1 10 0 259 210 11 2 10 0 77 5 43 3 10 0 97 83 21 1 11 0 348 359 13 2 11 0 86 11 31 3 11 0 236 225 17 4 11 0 288 303 23 0 12 0 585 527 37 1 12 0 283 234 12 2 12 0 344 321 15 3 12 0 88 37 25 4 12 0 169 156 21 1 13 0 38 9 37 2 13 0 97 124 22 3 13 0 168 188 18 4 13 0 88 4 40 0 14 0 105 104 19 1 14 0 164 161 11 2 14 0 123 93 11 3 14 0 89 139 27 4 14 0 0 50 1 1 15 0 83 60 30 2 15 0 248 227 10 3 15 0 283 273 15 0 16 0 77 26 25 1 16 0 40 24 40 2 16 0 63 39 23 3 16 0 62 93 61 1 17 0 50 8 50 2 17 0 58 46 57 3 17 0 114 143 14 0 18 0 100 100 25 1 18 0 122 122 27 2 18 0 65 44 29 3 18 0 67 21 37 1 19 0 67 82 34 2 19 0 86 77 15 3 19 0 44 9 43 0 20 0 188 199 19 1 20 0 0 42 1 3 0 1 336 325 28 4 0 1 0 25 1 −3 1 1 201 154 25 −2 1 1 116 114 8 −1 1 1 1143 962 30 0 1 1 134 157 3 1 1 1 1115 961 54 2 1 1 125 114 9 3 1 1 212 154 23 4 1 1 159 141 16 −3 2 1 441 430 24 −2 2 1 436 399 19 −1 2 1 1871 1484 56 0 2 1 142 155 3 1 2 1 1819 1485 117 2 2 1 432 400 28 3 2 1 453 431 34 4 2 1 117 84 36 −3 3 1 95 101 19 −2 3 1 356 355 23 −1 3 1 861 840 26 0 3 1 1901 1442 47 1 3 1 857 839 30 2 3 1 358 354 23 3 3 1 139 100 15 4 3 1 89 72 57 −4 4 1 146 157 30 −3 4 1 294 284 11 −2 4 1 334 364 20 −1 4 1 415 464 11 0 4 1 961 903 26 1 4 1 415 464 10 2 4 1 308 364 22 3 4 1 292 283 12 4 4 1 154 156 28 −3 5 1 218 162 21 −2 5 1 251 211 16 −1 5 1 621 673 26 0 5 1 143 120 6 1 5 1 624 673 16 2 5 1 214 212 19 3 5 1 193 163 11 4 5 1 97 32 53 −3 6 1 286 246 11 −2 6 1 179 174 25 −1 6 1 187 202 12 0 6 1 478 526 14 1 6 1 170 202 6 2 6 1 172 175 18 3 6 1 284 246 15 −3 7 1 122 113 11 −2 7 1 399 369 17 −1 7 1 317 373 10 0 7 1 185 170 7 1 7 1 313 372 9 2 7 1 368 369 28 3 7 1 128 112 17 4 7 1 146 100 24 −3 8 1 116 91 14 −2 8 1 104 93 13 −1 8 1 196 223 11 0 8 1 115 77 14 1 8 1 194 222 13 2 8 1 107 92 12 3 8 1 135 91 12 4 8 1 101 62 36 −3 9 1 114 91 17 −2 9 1 122 115 16 −1 9 1 522 569 22 0 9 1 556 610 16 1 9 1 513 570 22 2 9 1 126 116 11 3 9 1 79 92 30 −4 10 1 132 78 27 −3 10 1 195 194 19 −2 10 1 262 248 10 −1 10 1 375 400 14 0 10 1 690 690 21 2 11 1 322 300 23 3 11 1 63 25 49 −4 12 1 194 205 21 −3 12 1 232 275 22 −2 12 1 284 258 14 −1 12 1 522 526 18 0 12 1 680 694 30 1 12 1 509 525 23 2 12 1 260 268 9 3 12 1 285 275 14 4 12 1 198 205 20 −4 13 1 80 79 45 −2 13 1 91 91 13 −1 13 1 164 146 11 0 13 1 365 339 38 1 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1 5 5 63 68 8 2 5 5 120 109 23 3 5 5 70 52 38 4 5 5 130 148 35 −4 6 5 159 142 15 −3 6 5 294 243 11 −2 6 5 340 329 18 −1 6 5 562 622 22 0 6 5 941 879 28 1 6 5 569 622 15 2 6 5 351 329 23 3 6 5 263 243 13 4 6 5 127 142 38 −4 7 5 122 137 16 −3 7 5 297 305 13 −2 7 5 71 64 20 −1 7 5 376 436 24 0 7 5 389 456 14 1 7 5 394 436 11 2 7 5 64 65 64 3 7 5 312 305 13 4 7 5 132 137 34 −4 8 5 71 47 27 −3 8 5 111 96 17 −2 8 5 167 148 14 −1 8 5 335 365 21 0 8 5 532 614 16 1 8 5 346 365 22 2 8 5 120 148 30 0 10 3 74 69 14 1 10 3 197 178 10 2 10 3 245 211 9 3 10 3 183 188 14 4 10 3 95 59 41 −4 11 3 123 119 28 0 9 5 428 468 13 1 9 5 67 98 19 2 9 5 170 165 17 3 9 5 97 87 20 4 9 5 50 68 50 −4 10 5 80 79 56 −3 10 5 87 107 87 −2 10 5 136 116 23 −1 10 5 213 215 10 0 10 5 143 156 9 1 10 5 214 214 10 2 10 5 84 116 23 3 10 5 103 106 21 4 10 5 95 79 16 −4 11 5 0 47 1 −3 11 5 0 26 1 −2 11 5 264 252 9 −1 11 5 162 141 12 0 11 5 0 7 1 1 11 5 156 141 13 2 11 5 272 253 13 3 11 5 0 26 1 4 11 5 0 47 1 −4 12 5 0 40 1 −3 12 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11 20 68 63 26 3 11 20 61 67 25 −3 12 20 99 119 13 −2 12 20 183 201 14 −1 12 20 23 29 23 0 12 20 229 207 13 1 12 20 27 29 26 2 12 20 175 201 16 3 12 20 94 119 14 −3 13 20 179 177 12 −2 13 20 0 45 1 −1 13 20 266 252 9 0 13 20 61 71 60 1 13 20 246 252 13 2 13 20 44 45 43 3 13 20 136 178 12 −3 14 20 79 63 29 3 8 23 37 53 37 −3 9 23 161 147 11 −2 9 23 84 98 21 −1 9 23 233 221 9 0 9 23 254 229 15 1 9 23 232 221 12 2 9 23 117 98 19 3 9 23 118 146 12 −3 10 23 95 84 16 −2 10 23 106 77 24 −1 10 23 37 12 37 0 10 23 98 101 55 1 15 20 99 122 18 2 15 20 104 124 20 −2 16 20 99 78 23 −1 16 20 155 170 10 0 16 20 211 253 13 1 16 20 157 170 15 2 16 20 74 77 73 −2 17 20 62 55 25 −1 17 20 45 64 44 0 17 20 59 87 59 1 17 20 61 64 32 2 17 20 81 55 80 −2 18 20 59 46 31 −1 18 20 17 67 16 0 18 20 32 9 31 1 18 20 0 67 1 −1 19 20 108 80 12 0 19 20 23 13 22 1 19 20 61 80 60 0 20 20 42 75 42 1 0 21 0 49 1 2 0 21 44 18 43 3 0 21 75 75 21 4 0 21 0 37 1 −4 1 21 52 46 52 −3 1 21 95 96 40 −2 1 21 185 180 8 −1 1 21 96 67 29 0 1 21 315 327 11 1 1 21 80 66 23 2 1 21 178 181 7 3 1 21 111 97 14 4 1 21 88 46 22 −4 2 21 106 133 23 −3 2 21 210 218 12 −2 2 21 11 31 11 −1 2 21 40 89 40 0 2 21 92 74 14 1 2 21 90 88 13 2 2 21 53 31 21 3 2 21 206 218 24 4 2 21 122 133 10 −4 3 21 97 99 22 −3 3 21 104 107 29 −2 3 21 137 126 11 −1 3 21 71 63 19 0 3 21 177 170 15 1 3 21 91 64 22 2 3 21 131 125 7 3 3 21 91 107 16 4 3 21 109 99 10 −4 4 21 0 54 1 −3 4 21 34 49 33 −2 4 21 165 152 11 −1 4 21 115 97 15 0 4 21 71 61 21 1 4 21 116 97 11 2 4 21 163 152 7 3 4 21 68 49 21 4 4 21 61 54 20 −4 5 21 39 40 39 −3 5 21 104 122 14 −2 5 21 86 98 19 −1 5 21 347 332 10 0 5 21 94 55 26 1 5 21 346 332 12 2 5 21 96 98 10 3 5 21 99 123 11 4 5 21 22 40 22 −3 6 21 92 108 16 −2 6 21 164 136 11 −1 6 21 123 110 11 0 6 21 62 60 22 1 6 21 122 110 24 2 6 21 149 136 11 3 6 21 77 107 17 −3 7 21 0 41 1 −2 7 21 216 212 10 3 4 24 44 70 44 −3 5 24 63 90 28 −2 5 24 99 88 14 −1 5 24 86 54 20 0 5 24 150 118 11 1 5 24 75 54 24 2 5 24 102 88 17 3 5 24 58 90 25 −3 6 24 47 18 46 −2 6 24 134 112 11 −1 6 24 112 110 18 0 6 24 131 146 12 −3 9 21 150 159 13 −2 9 21 241 213 10 −1 9 21 174 127 9 0 9 21 155 152 11 1 9 21 151 126 11 2 9 21 195 212 13 3 9 21 133 159 11 −3 10 21 92 81 13 −2 10 21 110 77 14 −1 10 21 210 190 9 0 10 21 46 60 46 1 10 21 224 190 12 2 10 21 55 77 55 3 10 21 49 81 49 −3 11 21 44 18 43 −2 11 21 91 100 19 −1 11 21 62 47 30 0 11 21 424 384 21 1 11 21 0 47 1 2 11 21 99 100 15 3 11 21 41 19 41 −3 12 21 43 26 42 −2 12 21 43 51 43 −1 12 21 69 67 35 0 12 21 124 120 17 1 12 21 96 67 27 2 12 21 43 50 43 3 12 21 26 26 25 −3 13 21 45 60 45 −2 13 21 123 116 20 −1 13 21 178 164 10 0 13 21 268 241 13 1 13 21 178 164 17 2 13 21 108 116 15 3 13 21 73 61 21 −2 14 21 90 78 15 −1 14 21 78 75 20 0 14 21 41 87 40 1 14 21 65 75 29 2 14 21 98 78 21 −2 15 21 93 67 15 −1 15 21 71 71 22 0 15 21 106 118 20 1 15 21 73 71 40 2 15 21 89 67 88 −2 16 21 76 71 37 −1 16 21 65 84 24 0 16 21 22 46 21 1 16 21 94 84 19 2 16 21 83 70 27 −2 17 21 90 78 16 −1 17 21 95 112 14 0 17 21 76 38 27 1 17 21 129 112 18 2 17 21 113 78 22 −1 18 21 73 61 19 0 18 21 53 20 52 1 18 21 46 61 45 −1 19 21 25 17 24 0 19 21 135 143 18 1 19 21 50 17 49 0 20 21 109 48 28 0 0 22 390 413 19 1 0 22 41 23 40 2 0 22 230 213 10 3 0 22 210 222 23 4 0 22 72 84 71 −4 1 22 94 67 20 −3 1 22 140 162 63 −2 1 22 129 128 10 −1 1 22 132 125 10 0 1 22 273 267 13 1 1 22 111 126 20 2 1 22 135 128 9 3 1 22 141 162 11 2 1 25 179 164 18 3 1 25 100 95 16 −3 2 25 0 9 1 −2 2 25 60 14 50 −1 2 25 227 206 13 0 2 25 61 36 21 1 2 25 224 206 14 2 2 25 45 14 45 3 2 25 47 10 47 −3 3 25 45 39 44 −2 3 25 101 65 15 −1 3 25 91 91 31 0 3 25 70 5 18 1 3 25 110 92 21 2 3 25 51 65 36 −2 3 22 89 85 21 −1 3 22 124 99 11 0 3 22 162 174 9 1 3 22 105 98 13 2 3 22 97 85 18 3 3 22 92 112 14 4 3 22 100 96 16 −4 4 22 61 37 61 −3 4 22 59 59 28 −2 4 22 114 102 14 −1 4 22 75 70 26 0 4 22 85 60 17 1 4 22 68 70 20 2 4 22 86 102 13 3 4 22 0 60 1 −3 5 22 98 86 15 −2 5 22 50 41 49 −1 5 22 297 271 15 0 5 22 31 38 30 1 5 22 288 271 11 2 5 22 55 40 21 3 5 22 67 86 20 −3 6 22 108 109 16 −2 6 22 51 41 50 −1 6 22 22 49 21 0 6 22 230 213 8 1 6 22 80 49 33 2 6 22 0 41 1 3 6 22 112 109 11 −3 7 22 0 20 1 −2 7 22 119 135 14 −1 7 22 275 265 9 0 7 22 225 236 8 1 7 22 263 266 10 2 7 22 131 135 13 3 7 22 21 20 20 −3 8 22 99 103 15 −2 8 22 47 40 46 −1 8 22 171 139 9 0 8 22 163 159 20 1 8 22 150 138 13 2 8 22 68 40 28 3 8 22 77 104 16 −3 9 22 110 104 23 −2 9 22 200 176 10 −1 9 22 99 103 17 0 9 22 112 95 17 1 9 22 130 102 13 2 9 22 163 176 13 3 9 22 93 103 15 −3 10 22 218 222 13 −2 10 22 205 206 11 −1 10 22 58 34 36 0 10 22 63 25 62 1 10 22 57 35 56 2 10 22 166 206 12 3 10 22 168 222 15 −3 11 22 186 172 14 −2 11 22 181 191 12 −1 11 22 235 228 10 0 11 22 367 323 19 1 11 22 253 228 11 2 11 22 170 190 15 3 11 22 146 172 12 −3 12 22 38 64 37 −2 12 22 80 66 18 −1 12 22 81 94 20 0 12 22 14 50 13 1 12 22 127 95 14 2 12 22 57 66 36 3 12 22 56 64 31 −3 13 22 62 73 21 −2 13 22 126 163 12 −1 13 22 227 225 9 0 13 22 88 80 25 0 15 25 86 64 32 1 15 25 150 162 18 2 15 25 30 21 29 −1 16 25 31 46 31 0 16 25 148 190 22 1 16 25 59 45 58 −1 17 25 51 49 24 0 17 25 0 30 1 1 17 25 30 49 29 0 18 25 0 22 1 0 0 26 167 153 14 1 0 26 101 36 24 2 0 26 146 116 15 3 0 26 78 35 67 −3 1 26 56 48 29 2 15 22 305 318 17 −2 16 22 34 29 34 −1 16 22 115 110 12 0 16 22 125 114 16 1 16 22 146 110 17 2 16 22 59 29 59 −2 17 22 100 109 23 −1 17 22 118 143 11 0 17 22 35 33 35 1 17 22 177 143 14 −1 18 22 35 54 35 0 18 22 0 63 1 1 18 22 60 54 59 −1 19 22 0 9 1 0 19 22 24 13 23 1 0 23 84 17 17 2 0 23 175 163 9 3 0 23 73 22 43 −4 1 23 78 72 77 −3 1 23 99 101 43 −2 1 23 114 112 12 −1 1 23 103 92 24 0 1 23 66 102 54 1 1 23 117 93 12 2 1 23 119 112 11 3 1 23 100 101 14 4 1 23 124 71 28 −3 2 23 60 51 30 −2 2 23 232 221 15 −1 2 23 225 229 19 0 2 23 110 94 10 1 2 23 240 229 9 2 2 23 213 221 9 3 2 23 7 52 7 −3 3 23 96 95 16 −2 3 23 59 76 34 −1 3 23 61 66 29 0 3 23 294 260 13 1 3 23 92 65 17 2 3 23 91 77 13 3 3 23 108 94 12 −3 4 23 52 16 45 −2 4 23 173 156 10 −1 4 23 99 83 34 0 4 23 122 124 9 1 4 23 104 83 13 2 4 23 149 156 12 3 4 23 0 16 1 −3 5 23 61 66 29 −2 5 23 164 165 9 −1 5 23 219 183 16 0 5 23 64 76 20 1 5 23 205 182 9 2 5 23 156 164 12 3 5 23 60 66 24 −3 6 23 82 69 19 −2 6 23 122 111 12 −1 6 23 134 123 11 0 6 23 318 291 9 1 6 23 133 123 11 2 6 23 105 111 17 3 6 23 48 70 47 −3 7 23 45 16 45 −2 7 23 118 122 12 −1 7 23 162 146 9 0 7 23 63 48 26 1 7 23 161 145 14 2 7 23 120 122 14 3 7 23 0 16 1 −3 8 23 78 53 28 −2 8 23 63 22 24 −1 8 23 51 37 51 0 8 23 153 138 12 1 8 23 90 37 19 2 8 23 45 22 44 2 11 26 103 99 20 −2 12 26 79 78 20 −1 12 26 158 164 10 0 12 26 124 120 19 1 12 26 166 164 14 2 12 26 107 78 23 −2 13 26 110 97 14 −1 13 26 0 35 1 0 13 26 101 111 22 1 13 26 37 35 37 2 13 26 115 97 18 −2 14 26 28 34 27 −1 14 26 43 39 43 0 14 26 92 47 25 1 14 26 30 39 29 1 10 23 74 12 49 2 10 23 82 77 20 3 10 23 81 84 22 −3 11 23 108 114 34 −2 11 23 29 17 29 −1 11 23 206 176 9 0 11 23 108 83 40 1 11 23 202 176 12 2 11 23 0 17 1 3 11 23 114 114 18 −3 12 23 78 78 15 −2 12 23 137 139 11 −1 12 23 345 336 11 0 12 23 126 122 20 1 12 23 362 336 24 2 12 23 151 139 12 3 12 23 63 78 30 −2 13 23 95 107 15 −1 13 23 304 282 9 0 13 23 223 229 15 1 13 23 283 282 35 2 13 23 119 107 18 −2 14 23 103 105 14 −1 14 23 131 143 21 0 14 23 74 78 30 1 14 23 128 142 19 2 14 23 125 105 18 −2 15 23 63 76 24 −1 15 23 97 115 21 0 15 23 121 130 16 1 15 23 114 115 22 2 15 23 77 76 41 −2 16 23 99 94 21 −1 16 23 40 30 40 0 16 23 122 142 16 1 16 23 76 30 37 2 16 23 119 94 17 −1 17 23 79 107 17 0 17 23 57 42 56 1 17 23 93 107 24 −1 18 23 0 9 1 0 18 23 30 54 29 1 18 23 0 9 1 0 19 23 0 75 1 0 0 24 115 82 27 1 0 24 315 301 13 2 0 24 128 110 10 3 0 24 32 69 31 −3 1 24 68 70 23 −2 1 24 237 215 11 −1 1 24 171 84 58 0 1 24 31 37 30 1 1 24 114 84 13 2 1 24 230 216 11 3 1 24 38 70 37 −3 2 24 82 70 19 −2 2 24 271 286 10 −1 2 24 119 115 28 0 2 24 49 4 32 1 2 24 125 116 14 2 2 24 271 287 14 3 2 24 73 70 18 −3 3 24 0 47 1 −2 3 24 80 37 21 −1 3 24 344 300 20 0 3 24 89 73 13 1 3 24 324 300 12 2 3 24 27 37 26 3 3 24 41 47 41 −3 4 24 71 70 24 −2 4 24 134 124 11 −1 4 24 0 29 1 0 4 24 283 280 8 1 4 24 66 28 25 2 4 24 136 124 10 2 9 27 135 153 19 −2 10 27 51 59 51 −1 10 27 167 139 13 0 10 27 54 60 53 1 10 27 128 140 18 2 10 27 86 59 23 −2 11 27 49 69 49 −1 11 27 106 106 14 0 11 27 52 92 52 1 11 27 110 105 26 2 11 27 84 68 26 −2 12 27 86 125 36 −1 12 27 94 111 16 0 12 27 59 6 59 1 12 27 108 110 19 1 6 24 122 110 17 2 6 24 138 112 13 3 6 24 0 18 1 −3 7 24 67 69 24 −2 7 24 91 81 15 −1 7 24 130 111 15 0 7 24 154 165 10 1 7 24 104 111 17 2 7 24 70 80 26 3 7 24 76 69 16 −3 8 24 51 52 51 −2 8 24 142 145 12 −1 8 24 170 152 11 0 8 24 85 72 21 1 8 24 174 152 29 2 8 24 150 145 14 3 8 24 59 51 25 −3 9 24 40 19 40 −2 9 24 80 105 80 −1 9 24 102 86 15 0 9 24 126 97 21 1 9 24 128 85 22 2 9 24 108 105 20 3 9 24 0 18 1 −3 10 24 87 103 29 −2 10 24 105 122 14 −1 10 24 197 168 12 0 10 24 205 179 18 1 10 24 192 167 12 2 10 24 100 122 45 3 10 24 102 103 22 −3 11 24 13 7 12 −2 11 24 112 111 13 −1 11 24 112 117 14 0 11 24 212 204 15 1 11 24 125 118 25 2 11 24 80 111 33 3 11 24 67 7 23 −2 12 24 63 58 26 −1 12 24 126 81 23 0 12 24 54 74 53 1 12 24 109 80 15 2 12 24 60 58 59 −2 13 24 124 130 12 −1 13 24 275 287 9 0 13 24 70 57 46 1 13 24 266 287 34 2 13 24 141 130 15 −2 14 24 48 16 47 −1 14 24 152 138 17 0 14 24 42 46 42 1 14 24 137 138 20 2 14 24 78 16 30 −2 15 24 105 91 18 −1 15 24 167 203 11 0 15 24 218 194 14 1 15 24 222 203 14 2 15 24 131 91 16 −2 16 24 81 27 80 −1 16 24 61 75 44 0 16 24 0 18 1 1 16 24 74 75 34 −1 17 24 104 98 13 0 17 24 36 57 35 1 17 24 87 99 24 −1 18 24 54 56 53 0 18 24 0 52 1 1 0 25 122 111 15 2 0 25 82 34 18 3 0 25 200 195 17 −3 1 25 105 95 14 −2 1 25 202 164 9 −1 1 25 96 78 21 0 1 25 98 111 13 1 1 25 103 78 27 2 8 28 97 78 17 −2 9 28 55 73 39 −1 9 28 46 54 45 0 9 28 0 33 1 1 9 28 56 55 56 2 9 28 99 73 16 −2 10 28 74 81 21 −1 10 28 76 34 22 0 10 28 95 97 27 1 10 28 50 35 50 2 10 28 72 81 33 −2 11 28 61 48 30 −1 11 28 95 101 28 0 11 28 194 168 50 1 11 28 64 100 41 3 3 25 0 38 1 −3 4 25 84 90 33 −2 4 25 57 44 31 −1 4 25 185 172 15 0 4 25 272 278 9 1 4 25 175 172 12 2 4 25 54 45 27 3 4 25 85 90 15 −3 5 25 0 11 1 −2 5 25 118 114 12 −1 5 25 83 101 31 0 5 25 171 175 9 1 5 25 89 101 24 2 5 25 135 114 13 3 5 25 32 11 32 −3 6 25 101 68 24 −2 6 25 146 155 10 −1 6 25 104 89 20 0 6 25 107 83 16 1 6 25 122 88 14 2 6 25 128 154 14 3 6 25 77 69 17 −3 7 25 151 150 11 −2 7 25 136 111 12 −1 7 25 89 41 24 0 7 25 46 66 46 1 7 25 96 42 35 2 7 25 127 111 14 3 7 25 130 150 10 −3 8 25 49 60 49 −2 8 25 104 91 15 −1 8 25 191 203 11 0 8 25 26 43 26 1 8 25 200 202 15 2 8 25 101 91 16 3 8 25 80 59 18 −3 9 25 0 35 1 −2 9 25 20 45 20 −1 9 25 200 188 10 0 9 25 153 164 26 1 9 25 208 188 21 2 9 25 65 44 29 3 9 25 72 34 71 −3 10 25 68 73 34 −2 10 25 24 37 23 −1 10 25 132 115 12 0 10 25 101 79 27 1 10 25 114 116 54 2 10 25 81 37 20 3 10 25 75 73 20 −2 11 25 176 147 10 −1 11 25 334 282 10 0 11 25 92 85 30 1 11 25 289 282 19 2 11 25 137 147 16 −2 12 25 129 139 14 −1 12 25 119 110 12 0 12 25 132 113 20 1 12 25 109 111 49 2 12 25 156 139 14 −2 13 25 177 187 11 −1 13 25 78 77 20 0 13 25 222 210 28 1 13 25 64 77 64 2 13 25 198 188 13 −2 14 25 43 45 42 −1 14 25 179 177 9 0 14 25 244 266 15 1 14 25 184 176 17 2 14 25 0 44 1 −2 15 25 39 22 39 −1 15 25 178 162 9 0 9 29 95 67 19 1 9 29 0 2 1 2 9 29 0 24 1 −2 10 29 46 46 45 −1 10 29 161 167 10 0 10 29 79 35 22 1 10 29 163 167 61 2 10 29 0 46 1 −2 11 29 96 55 16 −1 11 29 97 79 15 0 11 29 143 97 17 1 11 29 82 79 26 2 11 29 0 54 1 −2 12 29 46 42 46 −1 12 29 17 49 16 0 12 29 227 193 18 1 12 29 0 49 1 −1 13 29 47 66 47 −2 1 26 76 80 20 −1 1 26 79 43 35 0 1 26 324 319 10 1 1 26 82 43 40 2 1 26 91 81 15 3 1 26 46 49 46 −3 2 26 119 132 13 −2 2 26 141 132 12 −1 2 26 159 105 15 0 2 26 146 129 10 1 2 26 126 104 20 2 2 26 141 132 13 3 2 26 117 133 11 −3 3 26 81 51 19 −2 3 26 68 79 22 −1 3 26 120 91 22 0 3 26 82 51 15 1 3 26 125 91 21 2 3 26 80 79 16 3 3 26 0 51 1 −3 4 26 146 112 20 −2 4 26 102 64 13 −1 4 26 181 168 15 0 4 26 78 62 26 1 4 26 161 168 16 2 4 26 61 64 22 3 4 26 107 113 13 −3 5 26 84 69 18 −2 5 26 166 151 10 −1 5 26 109 42 23 0 5 26 13 5 13 1 5 26 86 42 32 2 5 26 151 150 17 3 5 26 70 69 20 −3 6 26 70 26 22 −2 6 26 0 31 1 −1 6 26 195 185 15 0 6 26 127 131 14 1 6 26 183 184 15 2 6 26 6 31 5 3 6 26 0 26 1 −3 7 26 39 25 38 −2 7 26 86 59 19 −1 7 26 189 165 12 0 7 26 51 25 50 1 7 26 167 165 16 2 7 26 86 60 19 3 7 26 0 25 1 −3 8 26 87 75 17 −2 8 26 77 25 22 −1 8 26 46 39 46 0 8 26 72 52 32 1 8 26 0 40 1 2 8 26 40 25 39 3 8 26 97 74 15 −3 9 26 131 76 15 −2 9 26 61 80 30 −1 9 26 153 127 11 0 9 26 112 70 18 1 9 26 122 127 27 2 9 26 116 80 19 3 9 26 110 76 13 −3 10 26 114 34 42 −2 10 26 127 101 23 −1 10 26 99 71 21 0 10 26 107 117 25 1 10 26 100 72 23 2 10 26 107 101 16 −2 11 26 84 99 19 −1 11 26 169 176 13 0 11 26 63 119 62 1 11 26 167 176 29 −1 8 30 104 96 26 0 8 30 126 95 18 1 8 30 75 96 35 2 8 30 83 133 51 −2 9 30 0 51 1 −1 9 30 135 129 18 0 9 30 206 209 16 1 9 30 144 129 40 2 9 30 83 51 61 −2 10 30 30 20 29 −1 10 30 142 136 11 0 10 30 14 24 14 1 10 30 129 137 17 2 10 30 76 20 75 −2 11 30 50 33 50 −1 11 30 65 59 26 0 11 30 39 7 39 1 11 30 75 60 36 2 14 26 0 35 1 −1 15 26 74 57 19 0 15 26 132 124 17 1 15 26 69 57 38 −1 16 26 0 51 1 0 16 26 58 66 58 1 16 26 53 51 52 0 17 26 0 17 1 1 0 27 104 67 24 2 0 27 198 166 13 3 0 27 74 56 19 −3 1 27 124 125 12 −2 1 27 135 127 11 −1 1 27 124 129 20 0 1 27 136 123 11 1 1 27 142 129 18 2 1 27 155 127 18 3 1 27 141 125 12 −3 2 27 103 106 13 −2 2 27 106 87 15 −1 2 27 79 66 36 0 2 27 126 122 13 1 2 27 92 66 27 2 2 27 107 87 14 3 2 27 112 107 14 −3 3 27 168 152 15 −2 3 27 135 139 11 −1 3 27 229 239 14 0 3 27 98 100 27 1 3 27 226 240 30 2 3 27 116 140 13 3 3 27 143 151 11 −3 4 27 66 56 25 −2 4 27 110 112 15 −1 4 27 49 43 49 0 4 27 310 274 12 1 4 27 0 43 1 2 4 27 133 113 19 3 4 27 63 56 24 −3 5 27 0 41 1 −2 5 27 102 67 18 −1 5 27 191 175 16 0 5 27 69 18 29 1 5 27 192 174 32 2 5 27 64 67 62 3 5 27 16 41 16 −3 6 27 51 36 50 −2 6 27 176 182 12 −1 6 27 130 91 24 0 6 27 387 341 13 1 6 27 99 90 24 2 6 27 175 182 15 3 6 27 53 36 39 −3 7 27 51 32 51 −2 7 27 68 21 25 −1 7 27 183 175 10 0 7 27 265 251 12 1 7 27 160 174 16 2 7 27 21 21 21 3 7 27 31 32 30 −3 8 27 53 49 53 −2 8 27 200 206 10 −1 8 27 217 209 10 0 8 27 74 58 29 1 8 27 202 209 15 2 8 27 218 207 28 3 8 27 57 50 48 −3 9 27 0 69 1 −2 9 27 139 153 11 −1 9 27 114 126 14 0 9 27 194 140 15 1 9 27 117 126 28 −1 9 31 96 99 15 0 9 31 71 30 37 1 9 31 126 98 16 2 9 31 115 71 33 −1 10 31 63 62 28 0 10 31 87 85 20 1 10 31 84 62 25 −1 11 31 54 62 37 0 11 31 0 43 1 1 11 31 78 62 32 −1 12 31 15 13 14 0 12 31 0 33 1 1 12 31 0 14 1 −1 13 31 92 107 32 0 13 31 41 17 40 0 0 32 185 180 18 1 0 32 139 166 15 2 0 32 46 38 45 2 12 27 119 125 17 −2 13 27 0 53 1 −1 13 27 0 35 1 0 13 27 197 213 15 1 13 27 54 36 53 2 13 27 78 53 77 −1 14 27 56 65 31 0 14 27 60 31 60 1 14 27 0 65 1 −1 15 27 91 76 15 0 15 27 52 17 52 1 15 27 78 76 28 −1 16 27 28 22 27 0 16 27 110 119 27 1 16 27 38 23 38 0 0 28 376 331 19 1 0 28 132 99 21 2 0 28 49 36 49 3 0 28 71 71 19 −3 1 28 102 106 13 −2 1 28 97 67 24 −1 1 28 175 128 15 0 1 28 50 17 50 1 1 28 130 128 20 2 1 28 69 67 21 3 1 28 132 106 12 −3 2 28 108 116 13 −2 2 28 118 118 12 −1 2 28 129 127 31 0 2 28 70 11 27 1 2 28 151 126 16 2 2 28 107 117 12 3 2 28 139 117 12 −3 3 28 73 42 18 −2 3 28 184 168 13 −1 3 28 112 84 40 0 3 28 118 105 15 1 3 28 103 83 22 2 3 28 175 168 14 3 3 28 44 42 43 −3 4 28 179 161 10 −2 4 28 106 119 21 −1 4 28 150 182 17 0 4 28 459 389 15 1 4 28 168 182 14 2 4 28 157 119 23 3 4 28 158 161 12 −3 5 28 0 21 1 −2 5 28 123 125 14 −1 5 28 79 31 38 0 5 28 375 314 13 1 5 28 0 31 1 2 5 28 142 125 17 3 5 28 58 21 28 −3 6 28 0 50 1 −2 6 28 68 76 26 −1 6 28 268 259 13 0 6 28 69 25 28 1 6 28 225 259 18 2 6 28 53 76 53 3 6 28 55 50 55 −3 7 28 89 96 22 −2 7 28 136 124 12 −1 7 28 165 141 15 0 7 28 89 71 40 1 7 28 116 141 19 2 7 28 95 124 20 3 7 28 83 96 28 −2 8 28 96 78 23 −1 8 28 133 111 12 0 8 28 67 55 35 1 8 28 133 111 17 1 0 33 154 164 15 2 0 33 84 33 27 −2 1 33 122 104 20 −1 1 33 109 108 18 0 1 33 163 152 11 1 1 33 92 108 23 2 1 33 82 104 40 −2 2 33 97 78 15 −1 2 33 77 115 26 0 2 33 143 129 14 1 2 33 86 114 25 2 2 33 75 79 50 −2 3 33 0 33 1 −1 3 33 69 31 31 0 3 33 188 199 11 1 3 33 71 31 44 2 3 33 55 33 55 −2 4 33 92 73 19 2 11 28 46 48 46 −2 12 28 45 20 44 −1 12 28 60 35 30 0 12 28 167 159 16 1 12 28 67 36 48 2 12 28 0 20 1 −2 13 28 52 66 52 −1 13 28 114 133 13 0 13 28 57 7 57 1 13 28 99 133 24 −1 14 28 84 55 18 0 14 28 68 67 43 1 14 28 63 55 45 −1 15 28 130 131 12 0 15 28 0 25 1 1 15 28 117 132 17 0 16 28 0 31 1 1 0 29 227 220 29 2 0 29 87 76 15 3 0 29 59 59 26 −3 1 29 52 54 51 −2 1 29 135 139 24 −1 1 29 110 51 20 0 1 29 37 28 36 1 1 29 74 51 36 2 1 29 124 140 10 3 1 29 87 54 20 −3 2 29 109 104 12 −2 2 29 126 88 14 −1 2 29 301 291 33 0 2 29 120 99 17 1 2 29 252 291 26 2 2 29 90 88 13 3 2 29 126 104 14 −3 3 29 114 124 12 −2 3 29 70 42 27 −1 3 29 62 38 61 0 3 29 297 282 11 1 3 29 55 39 55 2 3 29 0 41 1 3 3 29 113 124 15 −3 4 29 50 73 50 −2 4 29 53 60 53 −1 4 29 94 90 25 0 4 29 84 62 22 1 4 29 113 90 18 2 4 29 70 59 24 3 4 29 82 73 17 −3 5 29 105 108 15 −2 5 29 173 154 17 −1 5 29 238 233 25 0 5 29 46 23 46 1 5 29 215 234 14 2 5 29 128 154 18 3 5 29 81 108 22 −2 6 29 0 24 1 −1 6 29 0 44 1 0 6 29 129 150 15 1 6 29 0 43 1 2 6 29 61 24 56 −2 7 29 69 52 29 −1 7 29 66 50 32 0 7 29 189 159 12 1 7 29 0 50 1 2 7 29 62 52 30 −2 8 29 53 59 53 −1 8 29 45 16 45 0 8 29 87 59 33 1 8 29 53 16 52 2 8 29 54 60 53 −2 9 29 68 24 25 −1 9 29 17 2 17 1 5 34 111 115 19 −1 6 34 68 61 28 0 6 34 0 17 1 1 6 34 107 62 20 −1 7 34 60 72 36 0 7 34 37 52 37 1 7 34 61 73 61 −1 8 34 0 37 1 0 8 34 100 86 17 1 8 34 73 37 32 −1 9 34 81 62 21 0 9 34 0 42 1 1 9 34 78 62 33 0 10 34 83 63 27 1 0 35 0 6 1 −1 1 35 61 24 54 0 1 35 89 39 25 1 1 35 62 24 45 0 13 29 0 42 1 1 13 29 81 66 28 −1 14 29 97 92 21 0 14 29 55 26 54 1 14 29 92 92 21 0 15 29 0 30 1 0 0 30 95 91 28 1 0 30 12 14 12 2 0 30 144 143 13 3 0 30 104 93 16 −3 1 30 70 70 27 −2 1 30 71 120 70 −1 1 30 203 200 32 0 1 30 54 39 54 1 1 30 182 200 38 2 1 30 126 120 12 3 1 30 53 70 53 −3 2 30 49 33 48 −2 2 30 37 64 36 −1 2 30 143 136 23 0 2 30 146 144 12 1 2 30 106 136 20 2 2 30 63 64 23 3 2 30 52 33 51 −3 3 30 0 21 1 −2 3 30 54 63 49 −1 3 30 57 68 56 0 3 30 300 302 11 1 3 30 43 68 43 2 3 30 0 63 1 −2 4 30 134 121 16 −1 4 30 99 113 27 0 4 30 229 206 10 1 4 30 98 113 19 2 4 30 85 121 29 −2 5 30 110 114 17 −1 5 30 78 81 22 0 5 30 125 120 14 1 5 30 52 81 52 2 5 30 105 114 20 −2 6 30 135 142 13 −1 6 30 109 121 15 0 6 30 47 48 47 1 6 30 111 121 18 2 6 30 121 142 33 −2 7 30 63 54 33 −1 7 30 70 95 23 0 7 30 70 45 30 1 7 30 77 95 28 2 7 30 64 54 44 −2 8 30 130 134 14 −1 12 30 46 54 45 0 12 30 34 25 34 1 12 30 40 55 40 −1 13 30 72 88 34 0 13 30 0 4 1 1 13 30 69 87 33 −1 14 30 85 87 33 0 14 30 33 10 33 1 0 31 23 11 23 2 0 31 128 146 14 −2 1 31 123 115 15 −1 1 31 159 177 28 0 1 31 187 200 15 1 1 31 173 177 21 2 1 31 108 116 15 −2 2 31 72 95 24 −1 2 31 0 79 1 0 2 31 25 15 24 1 2 31 87 79 24 2 2 31 56 94 55 −2 3 31 165 165 18 −1 3 31 71 87 32 0 3 31 103 113 20 1 3 31 88 86 31 2 3 31 117 166 19 −2 4 31 126 122 13 −1 4 31 69 68 36 0 4 31 103 87 18 1 4 31 100 69 20 2 4 31 110 122 19 −2 5 31 109 93 15 −1 5 31 159 179 32 0 5 31 0 25 1 1 5 31 167 178 14 2 5 31 0 93 1 −2 6 31 140 145 13 −1 6 31 80 33 21 0 6 31 167 181 12 1 6 31 42 33 41 2 6 31 151 145 34 −2 7 31 78 57 22 −1 7 31 77 100 48 0 7 31 142 140 12 1 7 31 86 99 34 2 7 31 0 57 1 −2 8 31 0 37 1 −1 8 31 88 88 20 0 8 31 74 23 27 1 8 31 100 88 70 2 8 31 0 37 1 −2 9 31 83 71 22 −2 1 32 128 126 12 −1 1 32 92 124 21 0 1 32 105 106 17 1 1 32 98 124 21 2 1 32 125 126 24 −2 2 32 77 79 25 −1 2 32 63 50 39 0 2 32 93 84 19 1 2 32 69 50 36 2 2 32 62 79 61 −2 3 32 181 163 11 −1 3 32 66 70 36 0 3 32 34 39 34 1 3 32 77 70 30 2 3 32 121 163 30 −2 4 32 81 70 21 −1 4 32 225 263 11 0 4 32 96 98 20 1 4 32 219 263 14 2 4 32 89 71 24 −2 5 32 42 55 41 −1 5 32 96 113 19 0 5 32 138 131 14 1 5 32 104 113 45 2 5 32 0 55 1 −2 6 32 61 30 32 −1 6 32 134 146 12 0 6 32 96 116 17 1 6 32 145 146 15 2 6 32 0 30 1 −2 7 32 49 23 49 −1 7 32 99 115 18 0 7 32 106 82 52 1 7 32 115 115 17 2 7 32 0 23 1 −2 8 32 50 83 49 −1 8 32 81 91 21 0 8 32 70 38 28 1 8 32 82 90 28 2 8 32 112 83 33 −1 9 32 36 39 35 0 9 32 50 68 50 1 9 32 65 39 42 −1 10 32 60 63 29 0 10 32 25 31 24 1 10 32 63 63 63 −1 11 32 80 66 19 0 11 32 0 42 1 1 11 32 19 66 19 −1 12 32 0 42 1 0 12 32 55 87 54 −1 4 33 112 140 14 0 4 33 78 75 24 1 4 33 148 139 23 2 4 33 27 74 26 −2 5 33 82 76 19 −1 5 33 120 120 17 0 5 33 80 57 23 1 5 33 133 121 17 2 5 33 77 76 77 −2 6 33 20 19 19 −1 6 33 0 42 1 0 6 33 65 61 32 1 6 33 55 42 54 2 6 33 0 20 1 −1 7 33 111 112 14 0 7 33 69 44 29 1 7 33 137 111 18 −1 8 33 62 73 33 0 8 33 6 18 5 1 8 33 82 74 27 −1 9 33 69 70 27 0 9 33 63 27 63 1 9 33 0 70 1 −1 10 33 8 50 8 0 10 33 48 11 48 1 10 33 46 50 45 0 11 33 132 125 13 0 0 34 254 258 25 1 0 34 57 41 56 2 0 34 0 45 1 −2 1 34 51 20 50 −1 1 34 120 141 17 0 1 34 150 131 13 1 1 34 131 141 17 2 1 34 33 20 32 −2 2 34 84 76 26 −1 2 34 92 103 21 0 2 34 123 120 15 1 2 34 103 103 20 2 2 34 0 76 1 −2 3 34 51 39 50 −1 3 34 95 103 17 0 3 34 161 176 24 1 3 34 101 103 21 2 3 34 0 39 1 −2 4 34 42 45 42 −1 4 34 107 135 15 0 4 34 75 89 37 1 4 34 130 135 34 −1 5 34 115 116 14 0 5 34 0 4 1 −1 2 35 75 63 74 0 2 35 0 71 1 1 2 35 106 63 21 −1 3 35 0 30 1 0 3 35 96 80 20 1 3 35 0 30 1 −1 4 35 89 93 19 0 4 35 0 18 1 1 4 35 109 93 21 −1 5 35 46 50 45 0 5 35 0 6 1 1 5 35 27 49 26 −1 6 35 107 115 16 0 6 35 70 54 27 1 6 35 126 115 17 −1 7 35 0 56 1 0 7 35 77 84 24 1 7 35 48 56 48 −1 8 35 80 26 38 0 8 35 46 50 46 0 9 35 0 7 1 0 0 36 97 106 35 1 0 36 55 1 55 −1 1 36 23 76 22 0 1 36 28 24 28 1 1 36 0 76 1 −1 2 36 0 26 1 0 2 36 49 87 48 1 2 36 41 25 40 −1 3 36 56 32 47 0 3 36 84 38 25 1 3 36 0 32 1 −1 4 36 78 49 29 0 4 36 23 16 23 1 4 36 0 49 1 −1 5 36 55 40 55 0 5 36 44 40 43 1 5 36 51 40 51 0 6 36 85 58 23 0 7 36 88 105 22 1 0 37 87 62 26 −1 1 37 75 69 62 0 1 37 68 67 37 1 1 37 82 69 35 −1 2 37 24 56 24 0 2 37 13 29 12 0 3 37 121 103 17 0 4 37 167 153 13 0 5 37 48 60 47

Example 2 Synthesis of 051810

The preparation of 051810 having the basic structure I can be accomplished by a common general method, i.e. the condensation of a bicyclic Windaus-Grundmann type ketone II with the allylic phosphine oxide III to the corresponding 2-methylene-19-nor-vitamin D analog IV followed by deprotection at C-1 and C-3 in the latter compound IV to obtain compound I, i.e. 051810.

In phosphine oxide III, Y₁ and Y₂ are preferably hydroxy-protecting groups such as silyl protecting groups. The t-butyldimethylsilyl (TMDMS) group is an example of a particularly useful hydroxy-protecting group. The process described above represents an application of the convergent synthesis concept, which has been applied effectively to the preparation of numerous vitamin D compounds (see Lythgoe et al., J. Chem. Soc. Perkin Trans. I, 590 (1978); Lythgoe, Chem. Soc. Rev. 9, 449 (1983); Toh et al., J. Org. Chem. 48, 1414 (1983); Baggiolini et al., J. Org. Chem. 51, 3098 (1986); Sardina et al., J. Org. Chem. 51, 1264 (1986); J. Org. Chem. 51, 1269 (1986); DeLuca et al., U.S. Pat. No. 5,086,191; DeLuca et al., U.S. Pat. No. 5,536,713; and DeLuca et al, U.S. Pat. No. 5,843,928 all of which are hereby incorporated by reference in their entirety and for all purposes as if fully set forth herein.

Phosphine oxide III is a convenient reagent that can be used to prepare a large number of 19-nor-vitamin D compounds and is prepared according to the procedures described by Sicinski et al., J. Med. Che., 41, 4662 (1998), DeLuca et al., U.S. Pat. No. 5,843,928; Perlman et al., Tetrahedron Let. 32, 7663 (1991); and DeLuca et al., U.S. Pat. No. 5,086,191 which are hereby incorporated by reference in their entirety as if fully set forth herein.

The overall process of the synthesis of compound I is illustrated and described more completely in U.S. Pat. No. 5,843,928 entitled “2-Alkylidene-19-Nor-Vitamin D Compounds” and in U.S. Pat. No. 7,238,681, entitled “2-Methylene-18,19-Dinor-1α-Hydroxy-Homopregnacalciferol and Its Uses” the specifications of which are specifically incorporated herein by reference. 

We claim:
 1. 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol in crystalline form.
 2. The crystalline form of 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol having molecular packing arrangement defined by space group P2 and unit cell dimensions a=4.8 Å, b=22.9 Å, c=36.1 Å, α=90°, β=90° and γ=90°.
 3. A three dimensional structure for 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol as defined by the molecular packing arrangement set forth in claim
 2. 4. A method of purifying 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol, comprising the steps of: (a) dissolving a product containing 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol to be purified in a solvent comprising ethyl acetate; (b) adding hexane to said solvent and dissolved product to form a mixture; (c) cooling said mixture containing said dissolved product below ambient temperature for a sufficient amount of time to form a precipitate of 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol crystals; and (d) separating the 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol crystals from the mixture.
 5. The method of claim 4 wherein the step of separating comprises filtering the mixture and precipitate to obtain the crystals.
 6. The method of claim 4 including a further step (d) comprising repeating steps (a) through (c) using the recovered crystals from step (c) as the product of step (a).
 7. The method of claim 4 wherein a ratio of ethyl acetate and hexane is about 1:99, by volume.
 8. A method of preparing 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol crystals by diffusive exchange of solvents, comprising the steps of: (a) dissolving a product containing 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol in a first solvent comprising benzene; (b) providing a second solvent comprising hexane; (c) allowing said first solvent with dissolved product and said second solvent to diffuse together for a sufficient amount of time to form a precipitate of 1α-hydroxy-2-methylene-18,19-dinor-homopregnacalciferol crystals; and (d) recovering the 1α-hydroxy-2-methyelene-18,19-dinor-homopregnacalciferol crystals.
 9. The method of claim 8 wherein a ratio of benzene and hexane is about 13:87, by volume.
 10. The method of claim 8 wherein the step of recovering comprises filtering to obtain the crystals.
 11. The method of claim 8 wherein the step of allowing said first solvent with dissolved product and said second solvent to diffuse together takes place in a closed system purged with argon.
 12. The method of claim 8 wherein the step of allowing said first solvent with dissolved product and said second solvent to diffuse together takes place at room temperature. 